Plant protecting agent

ABSTRACT

ULV plant protecting arthropodicidal formulation comprising alkyl aryl polyglycol ether as further additives in addition to the active ingredient(s) dissolved in the mixture of alphatic hydrocarbons and sunflower oil. The formulation according to the invention has an initial contact angle on the plant surface of &gt;13°, after 20 minutes of &gt;6° and it is often 120 minutes still at least 2°.

This is a continuation-in-part of co-pending application Ser. No.07/459,773 filed on Jan. 12, 1990, now abandoned.

CROSS REFERENCE TO RELATED APPLICATION

This application is a national phase application of PCT/HU 89/00012filed Apr. 7, 1989 and based upon Hungarian national application 1723/88of Apr. 7, 1988 under the International Convention.

FIELD OF THE INVENTION

The invention relates to plant protecting anthropodicidal ULVformulations containing interfacial tension modifying materials asfurther additives.

BACKGROUND OF THE INVENTION

It is known that the LV (Low Volume) and ULV (Ultra Low Volume) sprayapplication methods are the most advantageous and economical methods forplant and forest protection. These formulations are applied in a verysmall amount (5 l/ha) without dilution or in a low aqueous dilution(5-100 l/ha) instead of the common high rate (600 l/ha) or medium rate(100-600 l/ha) dilutions (Matthews G. A.: Pest management, 1984,Longman, London and New York). The advantage of said treatments is thatno water is required to prepare the spray and sometimes the ULVformulations are more active than the emulsion concentrates containingthe same dose of active ingredient (J. Econ. Entomol., 1986, 79:202).

However the treatments using a preparation in an amount less than 5 l/ha(i.e. the ULV treatments) can ensure the suitable coverage--which inturn ensures the effective control of the pests--only if the spraying iscarried out in a correct, optimal drop size distributin. The optimaldrop size plays very often a more important role than the dose used (J.Econ. Entomol., 1987. 80:460). Therefore special spray heads aregenerally used (e.g. Unirot, Autorot, Beecomist, MicroMax (DR4, Flak).The formulations are generally used without dilution and the activeingredient are dissolved in vegetable and/or mineral oils.

As mineral oil a mixture of aliphatic and aromatic hydrocarbons is used.The viscosity of the mineral oil does not exceed the value of 50 cP andthe flash point is above 60° C. (e.g. paraffin oil, Risella 917,Solvesso 200, HAN, Exxsol D 60).

The efficiency of the contact insecticides is also influenced by thedurability of the drop to be found on the surface of the plant. The oilsused in the ULV formulations spread gradually on the surface thenpenetrate into the epicuticular layer of wax of the plant. By this meansthe contact surfaces between the plant and the spray drop--and so theactual surfaces for the resorption of the active ingredient into theplant--are increased, however the specific dose "available" for theinsects may decrease which may slow down the intoxication.

It is known that the efficiency of the permethrin used in form of oilyULV formulation can be positively influenced by the retention time ofthe drop to be found on the surface of the leaf which can be followed bythe change of the wetting angle (contact angle) (Pestic. Sci. 1984,15:382). The wetting angle depends on the surface tension of the solidand liquid phases, on the interfacial tension and on the surfaceroughness (Szanto, P: The basis of the Collidal Chemistry, 1987,Publisher: Gondolat, Budapest).

SUMMARY OF THE INVENTION

The invention relates to ULV plant protecting anthropodicidalformulations suitable for application in a very small amount, comprising0.5-30 g/l of synthetic pyrethroids and/or phosphoric acid esters,thiophosphoric acid esters and/or dithiophosphoric acid esters in anamount of 0.5-300 g/l dissolved in a mixture comprising 2-300 g/laliphatic hydrocarbons, and sunflower oil in an amount necessary toreach 1000 ml and comprising further alkylaryl polyglycol ether in anamount of 2-100 g/l, preferably 15-60 g/l as an additive ensuring thatthe initial wetting (contact) angle of the formulation on the plantsurface is greater than 13°, it is greater than 6° after 20 minutes andit is at least 2° after 120 minutes.

DETAILED DESCRIPTION OF THE INVENTION

The aim of our invention is to provide spray drops having a lengthenedretention time by influencing the above mentioned factors and thereby toimprove the efficacy of the ULV formulations.

The present invention is based on the recognition that the efficacy ofcertain ULV compositions in oil or in mixture of oils can be enhanced ifsaid compositions contain suitable components for the modification ofthe penetration. The known ULV formulations used without dilution do notcontain additives tensides for decreasing the interfacial tension.

The invention relates to ULV plant protecting anthropodicidalformulations suitable for application in a very small amount, comprising0.5-30 g/l of synthetic pyrethroids, and/or phosphoric acid esters,thiophosphoric acid esters and/or dithiophosphoric acid esters in anamount of 0.5-300 g/l, dissolved in a mixture comprising 2-300 g/laliphatic hydrocarbons and sunflower oil in an amount necessary to 1000ml and comprising further alkylaryl polyglycol ether in an amount of2-100 g/l, preferably 15-60 g/l as additive ensuring that the initialwetting (contact) angle of the formulation on the plant surface isgreater than 13°, it is greater than 6° after 20 minutes and it is atleast 2° after 120 minutes.

The formulations according to the invention contain the followingnatural or synthetic pyrethroids: allethrin, bifenthrin, bioallethrin,bioresmethrin, chinmix, cyfluthrin, cyhalothrin, cypermethrin,deltamethrin, fenpropethrin, fenvalerate, flycythrinate, fluvalinate,permethrin, phenothrin, resmethrin, tetramethrin, tralomethrin, and/ortransmix.

The formulations according to the invention contain the followingphosphoric acid esters: trichlorfon, propaphos, dicrotophos,phosphamidon, profenophos; the following thiophosphoric acid esters:acephate, parathion, methylparathion, chlorpyriphos, methamidophos,demeton, oxy-demeton-methyl, fenitrotion, EPN, triazophost,pirimiphos-ethyl, mevinphos, quinalpos, fenthion, pirimiphos-methyland/or the following dithiophosphoric acid esters: dimethoate,azinphos-methyl, azinphos-ethyl, phosmet, malathion, phenthoate,methidathion and/or phosalon.

In the formulation according to the invention preferably nonylphenolpolyglycol ether (EO=6-10) is used as alkylaryl polyglycol ether and thealiphatic hydrocarbon mixture is preferably a mixture of C₁₀₋₁₅hydrocarbons containing 45-50% raphthene and having a flash point higherthan 58° C.

The oil used in the preparation according to the invention is preferablya contamination-free, double-filtered sunflower oil (pharmacopeia).

Those compositions are the most effective which enable--due to themodifying components--the formation of such a contact angle which canensure the adhesion of the drops located on a vertical or horizontalplant surface or on a plant surface between said two geometricalpositions and can inhibit the absorption thereof within 2 hours.

The experimental data presented in the following Examples prove that theefficiency of these compositions surpasses that of the comparativecompositions containing no modifying compound.

The contact (wetting) angle depends on the interfacial tension betweenthe oil drop and the given plant surface further on the gravity relatedto the drop size (Pestic. Sci., 1987. 15:382) on the quality of the oil(Pestic. Sci., 1987. 20:241) and on different physical parameters, e.g.temperature, humidity (Pestic. Sci., 1987. 20:105). These all have aninfluence on the spreading of the drop and on the penetration of theactive ingredient into the epicuticular layer of wax.

In the following Examples the behavior of drops having a diameter of 80μm and prepared under constant physical parameters from a preferred oilmixture was examined on different plant surfaces in the presence ofdifferent penetration modifying materials used individually or inmixture.

During our experiments the mixtures of different vegetable oil, e.g.soya, rape, palm, sunflower oil and mineral oils, e.g. differentaromatic and aliphatic hydrocarbons and the mixtures thereof wereexamined as solvent mixtures. As plant surface the young foliage leavesof lucerne (Medicago saliva) and sunflower (Helianthus annus) were used.The contact angle and absorption time of the plant protecting ULVformulations were determined by an optical method and the retention timewas followed by the change of the contact angle in time.

It has been established that the contact angle of the solution obtainedby the use of the mixture of sunflower oil and mixed hydrogenatedaliphatic hydrocarbons is 7°-10°, however an even lower value (7°-1°)may be obtained by the use of other mixtures. Surprisingly even thepenetration time of the compositions having a relatively great contactangle (10°) is only 15-20 minutes. The penetration of the ULVformulations having a contact angle below 7° takes place very quickly,in 2-15 minutes.

Accordingly such solvent mixture was used as starting solvent whichshows--in the form of the ULV formulation--a contact angle of 7°-10°.The following composition meets this requirement:

0.5-30 g/l of pyrethroid and/or 0.5-300 g/l phosphoric acid ester

2-300 g/l of aliphatic hydrocarbon mixture sunflower oil to 1000 ml.

Using the above composition the contact angle measured on the surface ofthe plant model was 7°-10° and the penetration time was 15-20 minutes.

As aliphatic hydrocarbon mixture EXXSOL D 60™ and EXXSOL D 100™ products(mixture of C₁₀₋₁₅ hydrocarbons, naphthene content: 45-50%, flash point:50°-100° C.) was used.

Exxsol® D 60 has the following characteristics:

    ______________________________________                                        Appearance, Visual      Bright & Clear                                        Aromatics Content, Liquid Chroma-                                                                      1.0 Max.                                             tography, Vol %                                                               Color, Saybolt, ASTM D 156                                                                           +30 Min.                                               Corrosion, Copper Strip, ASTM                                                                          1 Max.                                               D 130 3 hours at 100° C.                                               Distillation, ASTM D 86, °C.                                           Initial Boiling Point   182 Min.                                              50% Recovered           190-196                                               Dry Point               213 Max                                               Flash Point, ASTM D 56, °C.                                                                     60 Min.                                              Sulfur Content, ASTM D 3120, ppm                                                                       5 Max.                                                                             ASTM Test                                       VOLATILITY                                                                    Distillation, °C. (°F.)                                                                       D 86                                            IBP                  183 (362)                                                5%                   187 (368)                                                10%                  188 (370)                                                50%                  193 (379)                                                90%                  203 (397)                                                95%                  206 (403)                                                DPT                  211 (411)                                                Flash, TCC, °C. (°F.)                                                                 61 (141)                                                                              D 56                                            Evaporation, secs.            D 3539                                          50 vol. %             4000                                                    95 vol. %            10200                                                    Relative evaporation (NBA)                                                                         0.06     D 3539                                          SOLVENCY                                                                      Aniline Pt, °C. (°F.)                                                                69 (156) D 611                                           Kauri-butanol value  32.5     D 1133                                          Solubility Parameter  7.6     Calculated                                      COMPOSITION, VOLUME %         (a)                                             Aromatics             0.5                                                     Naphthenes           55.5                                                     Paraffins            44                                                       Benzenes             <0.01                                                    GENERAL                                                                       Auto Ignition Temp., °C. (°F.)                                                       227 (440)                                                                              E 659                                           Color, Saybolt       +30+     D 156                                           Copper corrosion     1A       D 130                                           3 hrs, @ 100° C. (212° F.)                                      Density, kg/L @ 15° C. (59° F.)                                                      0.792    D 1298                                          Gravity, °API 47.0     D 287                                           Non-Volatile Material, mg/100 mL                                                                   <1.0     D 1353                                          Refractive index @ 20° C. (68° F.)                                                   1.434    D 1218                                          Sulfur, Wt. ppm      <1       D 3120                                          Vapor Pressure, kPa (psia) @ 38° C.                                                         0.5 (0.07)                                                                             Calculated                                      Viscosity, mPa · s(cP) @ 25° C.                                                    1.24     D 445                                           ______________________________________                                         (a) by liquid chromatographic and mass spectrometric analysis            

EXXSOL D 60 Solvent is almost fully dearomatized. By severehydrogenation, the aromatics present in straight cut petroleum productare converted to naphthenes. Since naphthenes have better solvency thanstraight chain paraffins, the result is a product which better solvencythan would by achieved by simple removal of aromatics. Hydrogenationalso saturates olefins and removes impurities such as sulfur andhalogens to yield and extremely stable product.

TYPICAL PHYSICAL & CHEMICAL PROPERTIES FOR EXXSOL® D 60

SPECIFIC GRAVITY:

Not available

Density: 6.6 lbs/gal at 59

SOLUBILITY IN WATER, WT. % AT °F.:

Less than 0.10 at 68

SP. GRAV. OF VAPOR, at 1 atm (Air=1):

Greater than 1.00

EVAPORATION RATE, n-Bu Acetate=1:

0.1

VAPOR PRESSURE, mmHg at °F.:

3 at 100

VISCOSITY OF LIQUID, CST AT °F.:

2 at 77

FREEZING/MELTING POINT, °F.:

32 Below

BOILING POINT, °F.:

360 to 419

TYPICAL PHYSICAL & CHEMICAL PROPERTIES FOR EXXSOL® D 100

SPECIFIC GRAVITY:

Not Available

Density: 6.8 lbs/gal at 59

SOLUBILITY IN WATER, WT. % AT °F.:

Less than 0.10 at 68

SP. GRAV. OF VAPOR, At 1 atm (Air=1):

Greater than 1.00

EVAPORATION RATE, n-Bu Acetate=1:

Less than 0.0

VAPOR PRESSURE, mmHg at °F.:

0 at 100

Less than 1 at 131

VISCOSITY OF LIQUID, CST AT °F.:

3 at 77

2 at 104

FREEZING/MELTING POINT, °F.:

Less than -4

BOILING POINT, °F.:

462 to 511

The sunflower oil used was of pharmacopeia quality, double filtered.

Several additives modifying the interfacial behavior were examined indifferent concentration, and the contact angle and the change thereof intime was determined on the leaves of lucerne and sunflower plants.

The following materials were used as penetration modifying components:

Ionic type materials:

Ca salt of dodecylbenzenesulfonic acid,

Non-ionic type materials:

fatty alcohol polyglycol ethers: compounds of formula RX(CH₂ CH₂ O)_(y)H, wherein if X=0, then RO=cocoanut oil alcohol, oleyl alcohol, pine oilalcohol, isotridecyl alcohol;

alkyl-aryl polyglycol ethers, corresponding to the above generalformula, wherein if R is alkyl phenol then it stands for nonylphenol ortributylphenol and y=2-12,

fatty amine polyglycol ethers, wherein if X=NH then RNH is coconut oil,stearyl, oleyl, pine oil amine and y=2-12;

propylene oxide-ethylene oxide block polymer (EO=10-12)

It has been found that the ULV formulations corresponding to thefollowing composition:

0.5-30 g/l of pyrethroid and/or 0.5-300 g/l phosphoric acid ester,

2-300 g/l of mixed aliphatic hydrocarbon,

15-60 g/l of alkyl aryl polyglycol ether (EO=6-10) and

sunflower oil to 1000 ml,

have an initial contact angle on the surface of a plant model of13°-21°, after 20 minutes of 6°-10° and after 120 minutes of 2°-3° andit decreases to 0° only after 180 minutes.

When using any other additives in a concentration of 15-60 g/l or theformulation tested contains no additives, the initial contact angledetermined on the plant surfaces was smaller than 16° and 0° after 20minutes in case of lucerne and smaller than 8° in case of maize and 0°after 120 minutes in both cases.

It will be proved by the following Examples that the penetration time ofthe spray drops can significantly be increased by the use of the alkylaryl polyglycol ethers and this results in the significant increase ofthe efficiency of the active ingredient contained in the formulations.Due to this enhanced efficiency the specific dose (g activeingredient/ha) may be reduced which is very advantageous from point ofview of the costs of the plant protection and of the moderation of thepesticide-load. The active ingredients available for a longer time aspotent pesticides are further very advantageous as they may be utilizedto control the resistant populations.

The definitions of the abbreaviations used in the following Tables arethe following:

CIP=cypermethrin=alpha-cyano-3-phenoxy-benzyl-3-(2,2-dichlorovinyl)-2,2-dimethyl-cyclopropanecarboxylate

CHX="chinmix"=a mixture in a ratio of 40:60 of the following isomers ofcypermethrin: (IRcisS+1ScisR):1RtransS+1Strans==40:60

QUI=quinalphos=0,0-diethyl-0-chinoxalin-2-yl-phosphorothioate

DIA=diazinon=0,0-diethyl-0-2-isopropyl-6-methyl-pirimidin-4-yl-phosphorothioate

TRIA=triazophos=0,0-diethyl-0-1-phenyl-1H-1,2,4-triazol-3-yl-phosphorothioate

MET=methidathion=S-2,3-dihydro-5-methoxy-2-oxo-1,3,4-thiadiazol-3-yl-methyl-0,0-dimethylphosphorodithioate

HEPT=heptenophos=chlorobicyclo[3,2,0]hepta-2,6-dien-6-yl-dimethylphosphate

PHOS=phosalone=S-6-chloro-2,3-dihydro-2-oxobenzeneoxazol-3-yl-methyl-0,0-diethyl-phosphorodithioate

SF=synergistic factor

PBO=piperonyl butoxide

The invention is illustrated by the following Examples.

Example 1

    ______________________________________                                        Chinmix                     7.5    g/l                                        Exxsol D 100 ™           250    g/l                                        Sunflower oil     to        1000   ml                                         ______________________________________                                    

The composition is prepared by using a technology generally known forpreparing solutions, i.e. the sunflower oil is admixed with the Exxsol D100™ and the active ingredient is dissolved in the mixture obtained at15°-30° C., thereafter the solution is stirred for 30 minutes.

The contact angle is determined using a microscope having amagnification of 30x and equipped with an optical cross spider. Thedisplacement of the cross spider is determined by a fine scale angulardisplacement indicator.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      10°                                                                            6°                                              20. minute      0°                                                                            8°                                             120. minute      0°                                                                            0°                                             ______________________________________                                    

Example 2

    ______________________________________                                        Chinmix                     0.75   g/l                                        Exxsol D 100 ™           5      g/l                                        sunflower oil     to        1000   ml                                         ______________________________________                                    

The composition is prepared and the contact angle is determined asdescribed in Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      8°                                                                             4°                                              20. minute     0°                                                                             5°                                             120. minute     0°                                                                             0°                                             ______________________________________                                    

Example 3

    ______________________________________                                        Chinmix                       7.5    g/l                                      Nonylphenol polyglycol ether  60     g/l                                      (EO = 8)                                                                      Exxsol D 100 ™             250    g/l                                      sunflower oil        to       1000   ml                                       ______________________________________                                    

The composition is prepared by using the technology generally known forpreparing solutions, i.e. the sunflower oil is admixed with the Exssol D100™, thereafter the nonylphenol polyglycol ether is added, homogenizedand the active ingredient is dissolved in the mixture thus obtained. Thecontact angle is determined as described in Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      19°                                                                            21°                                             20. minute      6°                                                                            15°                                            120. minute      3°                                                                             6°                                            ______________________________________                                    

Example 4

    ______________________________________                                        Transmix                      0.75   g/l                                      Nonylphenol polyglycol ether  30     g/l                                      (EO = 8)                                                                      Exxsol D 100 ™             5      g/l                                      Sunflower oil        to       1000   ml                                       ______________________________________                                    

The composition is prepared as described in Example 3, and the contactangle is determined according to Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      19°                                                                            20°                                             20. minute      6°                                                                            15°                                            120. minute      2°                                                                             4°                                            ______________________________________                                    

Example 5

    ______________________________________                                        Chinmix                       7.5    g/l                                      Fatty alcohol polyglycol ether                                                                              60     g/l                                      (EO = 2)                                                                      Exxsol D 100 ™             250    g/l                                      Sunflower oil        to       1000   g/l                                      ______________________________________                                    

The composition is prepared as described in Example 3 and the contactangle is determined according to Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      9°                                                                             4°                                              20. minute     6°                                                                             2°                                             120. minute     0°                                                                             0°                                             ______________________________________                                    

Example 6

    ______________________________________                                        Chinmix                      7.5    g/l                                       Alkyl aryl polyglycol ether  30     g/l                                       (EO = 2)                                                                      Exxsol D 100 ™            250    g/l                                       Sunflower oil        to      1000   g/l                                       ______________________________________                                    

The composition is prepared as described in Example 3 and the contactangle is determined according to Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      8°                                                                             6°                                              20. minute     3°                                                                             0°                                             120. minute     0°                                                                             0°                                             ______________________________________                                    

Example 7

To a measuring flask of 1000 ml, 240 g quinalphos and 35 g nonylphenolpolyglycol ether (EO=10) are added and filled up to 1000 ml with the 1:5mixture (v/v) of Exxsol D 100™ and sunflower oil. The mixture obtainedis homogenized at 50° C. in the flask and after complete dissolution iscooled to 20° C. The contact angle is determined as described in Example1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      18°                                                                            20°                                             20. minute      9°                                                                            18°                                            120. minute      6°                                                                            11°                                            ______________________________________                                    

Example 8

In the mixture of 80 g piperonyl butoxide and 23 g nonylphenolpolyglycol ether (EO=10) 10 g chinmix and thereafter 240 g quinalphosare dissolved at 45° C. The solution thus obtained is filled up to 1000ml with the 1:6 mixture (v/v) of Exxsol D 60™ and sunflower oil.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      16°                                                                            18°                                             20. minute      8°                                                                            12°                                            120. minute      4°                                                                             8°                                            ______________________________________                                    

Example 9

    ______________________________________                                        Tetramethrin                  10     g/l                                      Nonylphenol polyglycol ether  60     g/l                                      (EO = 8)                                                                      Exxsol D 100 ™             250    g/l                                      Sunflower oil        to       1000   ml                                       ______________________________________                                    

The composition is prepared as described in Example 3 and the contactangle is determined according to Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      17°                                                                            23°                                             20. minute      7°                                                                            15°                                            120. minute      3°                                                                             7°                                            ______________________________________                                    

Example 10

    ______________________________________                                        Cypermethrin                  20     g/1                                      Nonylphenol polyglycol ether  15     g/l                                      (EO = 10)                                                                     Exxsol D 100 ™             200    g/l                                      Sunflower oil        to       1000   ml                                       ______________________________________                                    

The composition is prepared as described in Example 3 and the contactangle is determined according to Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      17°                                                                            24°                                             20. minute     11°                                                                            10°                                            120. minute      8°                                                                             8°                                            ______________________________________                                    

Example 11

    ______________________________________                                        Cypermethrin                  2      g/l                                      Nonylphenol polyglycol ether  20     g/l                                      (EO = 10)                                                                     Exxsol D 100 ™             48     g/l                                      Sunflower oil        to       1000   ml                                       ______________________________________                                    

The composition is prepared as described in Example 3 and the contactangle is determined according to Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      21°                                                                            23°                                             20. minute      7°                                                                            14°                                            120. minute      3°                                                                             9°                                            ______________________________________                                    

BIOLOGICAL EXAMPLES Example 12 Activity on potato beetle

Petri dishes (0 9 cm) are lined with potato leaves originated fromshoots which had not been treated with insecticides previously andsprayed with the compositions described above. The treatment is carriedout with a spraying machine (ULVA-system) modified for laboratorypurpose, having a rotating disc and equipped with a speed governor. Onan average 28 drops, having a diameter of 80 μm, are applied to everycm². After different drying time larvae of potato beetle (Leptinotarsadecemlienata SAY) of third larval stage are placed onto the treatedsurfaces and 5 hours later the number of the intoxicated, ataxic larvaeare determined. Four replicates, each using 15 larvae, are carried out.The results obtained and expressed in percentage are summarized in Table1.

                  TABLE 1                                                         ______________________________________                                        Drying time                                                                   after the         Compositions according to                                   spraying          Ex 1   Ex 3 Ex 5 Ex 6 Ex 8 Ex 10                            (min)    Control* knockdown %                                                 ______________________________________                                         0       0        70     100  70   75   100  100                               20      0        20      80  35   30   100  100                              120      0         0      50   5    0    85   90                              ______________________________________                                         *Composition according to Example 1, containing no active ingredient     

Example 13 Activity on the worms of fulvous clover

The treatments are carried out as described in Example 12, except thatsunflower leaves are used. After the different drying times worms offulvous clover (Heliothis maritima GRASLIN) of L₃ -L₄ larval stage,collected on field, are placed onto the treated leaves and 5 hours laterthe mortality is determined. The treatments are carried out in tworeplicates, each using 20 larvae. The results obtained are summarized inTable 2.

                  TABLE 2                                                         ______________________________________                                        Drying time                                                                   after the         Compositions according to                                   spraying          Ex 1   Ex 3 Ex 5 Ex 6 Ex 8 Ex 10                            (min)    Control* knockdown %                                                 ______________________________________                                         0       0        90     100  100  100  100  100                               20      0        30     100   35   40  100  100                              120      0         0      65   0    0   100  100                              ______________________________________                                         *Composition according to Example 1, containing no active ingredient.    

Example 14 Activity against plant-lice

The activity of the composition according to Example 3 is tested inindustrial scale in a 10 ha plot on winter wheat against plant lice.

A commercial composition, DECIS ULV is used as comparative composition.The application was carried out from helicopter at the time of milkystage (milky ripening) (at June 22) using a special ULV head. Theevaluation was carried out according to the Banks scale 2 and 7 daysafter the treatment using 8×25 marked ears. On the basis of the scalevalues the infection was calculated, thereafter the average number ofthe living individuals was expressed by the aid of an empirical table.The calculation of the percentage efficacy was made by theHenderson-Tilton equation.

                  TABLE 3                                                         ______________________________________                                                  Number of the living                                                                         efficacy in %                                                  individuals    (Henderson-                                                 dose before   2 days  7 days                                                                              Tilton)                                    Treatment                                                                              l/ha   treatment                                                                              after treatment                                                                         2. day                                                                              7. day                               ______________________________________                                        CYPERIL-S*                                                                             1.5    30.1     0.9   0.5   97.0  80.3                               DECIS ULV                                                                              1.5    30.8     1.4   1.0   95.6  62.7                               Untreated                                                                              --     26.9     28.0  2.4   --    --                                 control                                                                       ______________________________________                                         *Composition according to Example 3.                                     

Example 15

To a measuring flask of 1000 ml 400 g of Phosalone and 25 g ofnonylphenol polyglycol ether (EO=10) are added and filled up to 1000 mlwith the 1:1:5 mixture (v/v) of Solvesso 200, Exxsol D 100™ andsunflower oil. The mixture obtained is homogenized at 25° C.

The contact angle is determined as described in Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      18°                                                                            22°                                             20. minute     8°                                                                             18°                                            120. minute     6°                                                                              7°                                            ______________________________________                                    

Example 16

According to Example 15 the following composition is prepared:

    ______________________________________                                        Phenitrothion           300    g/l                                            Nonylphenol polyglycol ether                                                                          50     g/l                                            (EO = 8)                                                                      Exxsol D 100 ™       250    g/l                                            Sunflower oil to        1000   ml                                             ______________________________________                                    

The contact angle of the above preparation is determined as described inExample 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      22°                                                                            24°                                             20. minute     7°                                                                             15°                                            120. minute     4°                                                                              6°                                            ______________________________________                                    

Example 17

    ______________________________________                                        Malathion               300    g/l                                            Nonylphenol polyglycol ether                                                                          25     g/l                                            Solvesso 200            100    g/l                                            Exxsol D 100 ™       250    g/l                                            Sunflower oil to        1000   ml                                             ______________________________________                                    

The composition is prepared according to Example 15 and the contactangle is determined as described in Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      18°                                                                            21°                                             20. minute     6°                                                                             15°                                            120. minute     3°                                                                              7°                                            ______________________________________                                    

Example 18

    ______________________________________                                        Phosalone               400    g/l                                            Chinmix                 8      g/l                                            Nonylphenol polyglycol ether                                                                          15     g/l                                            (EO = 10)                                                                     Essxol D 100 ™       250    g/l                                            Sunflower oil to        1000   ml                                             ______________________________________                                    

The composition is prepared according to Example 15 and the contactangle is determined as described in Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting angle   lucerne sunflower                                             ______________________________________                                         0. minute      18°                                                                            20°                                             20. minute     7°                                                                             16°                                            120. minute     3°                                                                              7°                                            ______________________________________                                    

Example 19

    ______________________________________                                        Deltamethrin            5      g/l                                            Nonylphenol polyglycol ether                                                                          20     g/l                                            (EO = 10)                                                                     Solvessso 200           100    g/l                                            Exxsol D 100 ™       250    g/l                                            Sunflower oil to        1000   ml                                             ______________________________________                                    

The composition is prepared according to Example 15 and the contactangle is determined as described in Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      17°                                                                            18°                                             20. minute     7°                                                                             12°                                            120. minute     3°                                                                              9°                                            ______________________________________                                    

Example 20

    ______________________________________                                        Malathion               300    g/l                                            Deltamethrin            5      g/l                                            Nonylphenol polyglycol ether                                                                          20     g/l                                            (EO = 8)                                                                      Solvesso 200            100    g/l                                            Exxsol D 100 ™       250    g/l                                            Sunflower oil to        1000   ml                                             ______________________________________                                    

The composition is prepared according to Example 15 and the contactangle is determined as described in Example 1.

    ______________________________________                                                      Contact angle                                                   Wetting time    lucerne sunflower                                             ______________________________________                                         0. minute      21°                                                                            24°                                             20. minute     8°                                                                             15°                                            120. minute     4°                                                                              8°                                            ______________________________________                                    

What we claim is:
 1. An ultra-low volume plant-protectingarthropodicidal formulation, which comprises:(a) 0.5 to 30 g/l of apyrethroid selected from the group consisting of allethrin, bifenthrin,bioallethrin, bioresmethrin, a mixture in a ratio of 40:60 of thefollowing isomers of cypermethrin: 1RcisS+1ScisR:1RtransS+1StransR,cyfluthrin, cyhalothrin, cypermethrin, deltamethrin, fenpropethrin,fenvalerate, flycythrinate, fluvalinate, permethrin, phenothrin,resmethrin, tetramethrin, tralomethrin, and transmix; (b) 2 to 100 g/lof a nonylphenol polyglycol ether having an EO of 6 to 10; (c) 2 to 300g/l of a C₁₀ to C₁₅ aliphatic hydrocarbon mixture containing 45 to 50%naphthene and having a flash point of 50° to 100° C.; and (d) balancesunflower oil to 1000 ml, wherein the initial contact angle of theformulation on the plant surface is greater than 13°; after 20 minutes,is greater than 6°; and after 120 minutes is still at least 2°.
 2. TheULV plant-protecting arthropodicidal formulation defined in claim 1which comprises contamination-free, double-filtered sunflower oil. 3.The ULV plant-protecting arthropodicidal formulation defined in claim 1which further comprises; 0.5 to 300 g/l of a phosphoric acid ester,thiophosphoric acid ester, or dithiophosphoric acid ester.
 4. The ULVplant-protecting arthropodicidal formulation defined in claim 3 whereinthe phosphoric acid ester is selected from the group consisting oftrichlorforn, propaphos, dicrotophos, phosphamidon, profenophos, andcrotophos; the thiophosphoric acid ester is selected from the groupconsisting of acephate, parathion, methylparathion, chlorpyriphos,demeton, oxy-demethon-methyl, fenitrothion, EPN, triazophos,pirimiphos-methyl, mevinphos, quinalphos, and fenthion; and thedithiophosphopric acid ester is selected from the group consisting ofdimethoate, azinphos-methyl, azinphos-ethyl, phosmet, malathion,phentoate, methidathion, and phosalone.
 5. An ultra-low volumeplant-protecting arthropodicidal formulation, which comprises:(a) 0.75to 10 g/l of a pyrethroid selected from the group consisting of amixture in a ratio of 40:60 of the following isomers of cypermethrin:1RcisS+1ScrisR:1RtransS+1StransR, cypermethrin, deltamethrin,permethrin, tetramethrin, and transmix; (b) 15 to 60 g/l of anonylphenol polyglycol ether having an EO of 6 to 10; (c) 5 to 250 g/lof a C₁₀ to C₁₅ aliphatic hydrocarbon mixture containing 45 to 50%naphthene and having a flash point of 50° to 100° C.; and (d) balancesunflower oil to 1000 ml, wherein the initial contact angle of theformulation on the plant surface is greater than 13°; after 20 minutes,is greater than 6°; and after 120 minutes is still at least 2°.
 6. TheULV plant-protecting arthropodicidal formulation defined in claim 5which further comprises a compound selected from the group consisting ofquinalphos, phosalone and malathion.
 7. The ULV plant-protectingarthropodicidal formulation defined in claim 5 which comprises:(a) 7.5g/l of a mixture in a ratio of 40:60 of the following isomers ofcypermethrin: 1RcisS+1ScisR:1Rtrans+1StransR; (b) 60 g/l of nonylphenolpolyglycol ether having an EO equalling 8; (c) 250 g/l of a C₁₀ to C₁₅hydrocarbon mixture containing 45 to 50% naphthene having a flash pointhigher than 58° C.; and (d) balance sunflower oil up to 1000 ml.
 8. Aplant protection method which comprises spraying onto plants apesticidally effective amount of the ultra-low volume plant-protectingarthropodicidal formulation defined in claim 1.